System of selectively cleaning copper substrate surfaces, in-situ, to remove copper oxides

ABSTRACT

A system and method of selectively etching copper surfaces free of copper oxides in preparation for the deposition of an interconnecting metallic material is provided. The method removes metal oxides with β-diketones, such as Hhfac. The Hhfac is delivered into the system in vapor form, and reacts almost exclusively to copper oxides. The by-products of the cleaning process are likewise volatile for removal from the system with a vacuum pressure. Since the process is easily adaptable to most IC process systems, it can be conducted in an oxygen-free environment, without the removal of the IC from the process chamber. The in-situ cleaning process permits a minimum amount of copper oxide to reform before the deposition of the overlying interconnection metal. In this manner, a highly conductive electrical interconnection between the copper surface and the interconnecting metal material is formed. An IC having a metal interconnection, in which the underlying copper layer is cleaned of copper oxides, in-situ with Hhfac vapor, is also provided.

This application is a divisional application of Ser. No. 08/861,808,filed on May 22, 1997, entitled SYSTEM AND METHOD OF SELECTIVELYCLEANING COPPER SUBSTRATE SURFACES, IN SITU, TO REMOVE COPPER OXIDES,invented by Tue Nguyen, Lawrence Charneski, David Evans, and Sheng TengHsu.

BACKGROUND AND SUMMARY OF THE INVENTION

This invention relates generally to integrated circuit (IC) processesand fabrication, and more particularly, a system and method for cleaningcopper oxides from a copper IC surface, in-situ, to improve electricalconductivity between the copper and subsequently deposited conductivematerials.

The demand for progressively smaller, less expensive, and more powerfulelectronic products, in turn, fuels the need for smaller geometryintegrated circuits, and large substrates. It also creates a demand fora denser packaging of circuits onto IC substrates. The desire forsmaller geometry IC circuits requires that the interconnections betweencomponents and dielectric layers be as small as possible. Therefore,research continues into reducing the width of via interconnects andconnecting lines. The conductivity of the interconnects is reduced asthe surface area of the interconnect is reduced, and the resultingincrease in interconnect resistivity has become an obstacle in ICdesign. Conductors having high resistivity create conduction paths withhigh impedance and large propagation delays. These problems result inunreliable signal timing, unreliable voltage levels, and lengthy signaldelays between components in the IC. Propagation discontinuities alsoresult from intersecting conduction surfaces that are poorly connected,or from the joining of conductors having highly different impedancecharacteristics.

There is a need for interconnects and vias to have both low resistivity,and the ability to withstand volatile process environments. Aluminum andtungsten metals are often used in the production of integrated circuitsfor making interconnections or vias between electrically active areas.These metals are popular because they are easy to use in a productionenvironment, unlike copper which requires special handling.

Copper (Cu) is a natural choice to replace aluminum in the effort toreduce the size of lines and vias in an electrical circuit. Theconductivity of copper is approximately twice that of aluminum and overthree times that of tungsten. As a result, the same current can becarried through a copper line having half the width of an aluminum line.

The electromigration characteristics of copper are also much superior tothose of aluminum. Aluminum is approximately ten times more susceptiblethan copper to degradation and breakage through electromigration. As aresult, a copper line, even one having a much smaller cross-section thanan aluminum line, is better able to maintain electrical integrity.

There have been problems associated with the use of copper, however, inIC processing. Copper contaminates many of the materials used in ICprocesses and, therefore, care must be taken to keep copper frommigrating. Various means have been suggested to deal with the problem ofcopper diffusion into integrated circuit material. Several materials,particularly refractory metals, have been suggested for use as barriersto prevent the copper diffusion process. Tungsten, molybdenum, andtitanium nitride (TiN) are examples of refractory metals which may besuitable for use as copper diffusion barriers. However, the adhesion ofcopper to these diffusion barrier materials has been an IC processproblem, and the electrical conductivity of such materials is an issuein building IC interconnects.

Metal cannot be deposited onto substrates, or into vias, usingconventional metal deposition processes, such as sputtering, when thegeometries of the selected IC features are small. It is impractical tosputter metal, either aluminum or copper, to fill small diameter vias,since the gap fling capability is poor. To deposit copper, variouschemical vapor deposition (CVD) techniques are under development in theindustry.

In a typical CVD process, copper is combined with an organic ligand tomake a volatile copper compound or precursor. That is, copper isincorporated into a compound that is easily vaporized into a gas.Selected surfaces of an integrated circuit, such as diffusion barriermaterial, are exposed to the copper containing gas in an elevatedtemperature environment. When the volatile copper gas compounddecomposes, copper is left behind on the heated selected surface.Several copper compounds are available for use with the CVD process. Itis generally accepted that the molecular structure of the coppercompound, at least partially, affects the conductivity of the copperfilm residue on the selected surface.

Connections between metal levels, such as copper, which are separated bydielectric interlevels, are typically formed with a damascene method ofvia formation between metal levels. The underlying copper film is firstcompletely covered with the dielectric, a typical dielectric is silicondioxide. A patterned photoresist profile is then formed over thedielectric. The resist profile has an opening, or hole, in thephotoresist corresponding to the area in the dielectric where the via isto be formed. Other areas of the dielectric to be left in place arecovered with photoresist. The dielectric not covered with photoresist isthen etched to remove oxide underlying the hole in the photoresist. Thephotoresist is then stripped away. A thin film of copper, or some othermetallic material, is then used to fill the via. A layer consisting ofdielectric with a copper via through it now overlies the copper film.The excess copper remaining is removed with a chemical mechanical polish(CMP) process, as is well known in the art. The result is an “inlaid” ordamascene structure.

The deposition of copper using a CVD process often involves thedeposition of by-products on the copper surface. The copper is combinedwith ligands in the CVD precursor until deposition. As the copperdecomposes from the precursor, ligands, or parts of ligands, maydecompose in solid form, or combine with other materials in theenvironment, to degrade the copper film. In addition, the copper film isexposed to other IC material and etching processes which cover the filmwith by-products. These by-products must be removed to make a goodelectrical contact with subsequently deposited metal layers. As aresult, these copper films must be cleaned to improve electricalconductivity, before they can be interfaced with metallic contacts inthe IC.

A co-pending application, Ser. No. 08/717,267, filed Sep. 20, 1996,entitled, “Oxidized Diffusion Barrier Surface for the Adherence ofCopper and Method for Same”, invented by Tue Nguyen, Lawrence J.Charneski, and Lynn R. Allen, which is assigned to the same Assignees asthe instant patent, discloses a method for oxidizing the diffusionbarrier surface to improve the adherence of copper to a diffusionbarrier. In low speed electrical circuits the resistance offered by athin level of oxide is unnoticeable. However, in higher speedapplications even a small amount of resistance can increase thepropagation delay of electron current across an oxide layer. The primarypurpose of this, above mentioned, patent application is to improve theability of copper to remain deposited on a surface, not on improving theconductivity between copper and another surface.

Another co-pending application, Ser. No. 08/717,315, filed Sep. 20,1996, entitled, “Copper Adhered to a Diffusion Barrier Surface andMethod for Same”, invented by Lawrence J. Charneski and Tue Nguyen,which is assigned to the same Assignees as the instant patent, disclosesa method for using a variety of reactive gas species to improve copperadhesion without forming an oxide layer over the diffusion barrier.However, the focus of this patent is to improve copper adhesion, not toimprove the conductivity of copper deposited on a surface. In addition,the method of the above patent is generally only applicable to diffusionbarrier material.

Another co-pending application, Ser. No. 8/729,567, filed Oct. 11, 1996,entitled, “Chemical Vapor Deposition of Copper on an ION PreparedConductive Surface and Method for Same,” invented by Nguyen and Maa,which is assigned to the same Assignees as the instant patent, disclosesa method of preparing a conductive surface, such as copper, with anexposure to the ions of an inert gas to improve electrical conductivitybetween a conductive surface and a subsequent deposition of copper.However, the primary purpose of this invention is to prepare aconductive surface that is substantially free of by-products and ICprocess debris.

It would be advantageous to employ a method of cleaning a copper ICsubstrate surface while minimally exposing the surface to oxygen, tosuppress the formation of copper oxides on the surface.

It would be advantageous to employ a method of cleaning an IC substrateto selectively remove only copper oxides from a copper conductivesurface, minimizing the removal of copper from the copper conductivesurface.

It would be advantageous if a selective copper cleaning process used thevapor of a room temperature liquid which could be easily delivered intoan IC process system to volatilize copper oxides. In this manner, the ICwould not have to be removed from the chamber for cleaning and exposureto an oxygen atmosphere.

Accordingly, in an integrated circuit having a dielectric interlevelwith a dielectric surface, and a plurality of metal levels underlyingthe dielectric interlevel, a method for selectively cleaning metaloxides, in-situ, from a surface on a first metal level, accessed througha via from the dielectric surface, is provided. The method comprises thesteps of:

a) providing an atmosphere surrounding the integrated circuit;

b) controlling the atmosphere to be substantially free of oxygen,whereby the formation of metal oxides on the first metal level surfaceis minimized;

c) introducing a β-diketone vapor into the atmosphere; and

d) volatilizing the metal oxidizes from the first metal level surfaceusing the β-diketone vapor introduced in step c). A minimal amount ofmaterial is removed from the first metal level surface in preparationfor an electrical connection with subsequently deposited metal levels.

Typically, the first metal level surface is a metal selected from thegroup consisting of copper and silver. In one aspect of the invention,step c) includes using hexafluoroacetylacetonate (Hhfac) as theβ-diketone to volatilize the oxides on the conductive interlevelconnection surface.

In another aspect of the invention step c) includes delivering the Hhfacat a pressure of less than approximately 85 Torr and a temperature ofapproximately 20° C. The method typically includes the further step,following step d), of creating a vacuum to remove the volatile metaloxides obtained in step d) from the atmosphere. The volatile cleaningby-products are easily removed from the area of the IC by creating avacuum.

Another aspect of the invention includes the further step, before stepc), of controlling the IC temperature to be in the range between 100° C.and 450° C. The method includes the further step, following step d), of,while maintaining the atmosphere established in step b), depositing asecond metal level overlying the first metal level surface toelectrically interface to the first metal level. A cleaning processfacilitates a low resistance electrical connection. The second metallevel is a metal selected from the group consisting of TiN,TiSi_(x)N_(y), TaSi_(x)N_(y), TaN, WN, WSi_(x)N_(y), Ti, Ta, W, Cu, Al,Ag, and Au.

An integrated circuit is also provided comprising a dielectricinterlevel with a dielectric surface, and a plurality of metal levelsunderlying the dielectric interlevel. The integrated circuit furthercomprises a via from the dielectric surface to a first metal level, anda surface on the first interlevel. The first metal level surface isaccessed from the dielectric surface through the via. The first metallevel surface is prepared for subsequent overlying metal depositionswith a process for the selective, in-situ, cleaning the first metallevel surface of metal oxides with a β-diketone vapor, in an atmospherefree of oxygen. The metal oxides are removed with a minimal loss of thefirst metal level surface.

In an integrated circuit, including a dielectric interlevel with adielectric surface, and a plurality of metal levels underlying thedielectric interlevel, a system for the selective, in-situ, cleaning ofmetal oxides from a surface on a first metal level, accessed through avia from the dielectric surface to the first metal level, is provided.The system comprises a chamber to control an atmosphere to besubstantially free of oxygen, whereby the formation of metal oxides onthe first metal level surface is minimized. The system also comprises abubbler to introduce a β-diketone vapor into the chamber, and a waferchuck located inside the chamber and upon which the IC is mounted. Thewafer chuck has a predetermined temperature to control the temperatureof the IC, whereby the β-diketone volatilizes metal oxides on thesurface of the first metal, in preparation for electrical connection tosubsequently deposited metal levels.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1 through 4 illustrate steps in the formation of an IC with afirst metal level surface, prepared for a subsequent deposition of asecond metal level, with a process for the selective, in-situ, cleaningof the first metal level surface of metal oxides.

FIG. 5 is a representation of the keto-enol tautomerisms.

FIG. 6 illustrates a system for the selective, in-situ, cleaning ofmetal oxides from a surface on a first metal level of an integratedcircuit.

FIG. 7 is a graph illustrating the relationship of Hhfac vapor pressureversus inverse temperature.

FIG. 8 is a flow chart illustrating steps in a method for selectivelycleaning metal oxides, in-situ, from a surface on a first metal level.

DETAIL DESCRIPTION OF THE PREFERRED EMBODIMENT

FIGS. 1 through 4 illustrate steps in the formation of an IC with afirst metal level surface, prepared for a subsequent deposition of asecond metal level, with a process for the selective, in-situ, cleaningof the first metal level surface of metal oxides. The metal oxides arecleaned with a β-diketone vapor in an atmosphere free of oxygen. FIG. 1is a cross-sectional view of an IC 10. IC 10 consists of a dielectricinterlevel 12 with a dielectric surface 14, and a plurality of metallevels underlying dielectric interlevel 12. Dielectric interlevel 14 istypically an electrical insulator such as an oxide or nitride ofsilicon, fluorinated carbon, or parylene (F or N). Underlying dielectricinterlevel 12 is a barrier insulator layer 16, and underlying barrierinsulator layer 16 is a first metal level 18. First metal level 18 is ametal selected from the group consisting of copper and silver.Underlying first metal level 18 is a barrier metal layer 20, andunderlying barrier metal layer 20 is a layer of silicon 22.

A number of materials may be used in the dielectric interlevels andbarrier levels of IC 10, the materials chosen in FIG. 1, and thearrangement of the materials, are typical, but not exclusive, of thoseused in IC processes with first metal level 18. Barrier layers 16 and 20are not required to enable the invention, but are included when it isimportant to prevent the migration of metal atoms from first metal level18 to other sensitive IC circuit materials (not shown). IC 10 usuallyincludes a variety of coupled electrical components such as transistors,capacitors, and resistors. Further, IC 10 includes assemblies of theabove mentioned parts to create logic networks and integrated circuits.

FIG. 1 is the first step in a damascene process of formiing a metallicelectrical interconnection to first metal level 18. That is, a via is tobe formed from dielectric surface 14 to first metal level 18. One methodof forming the via is to cover dielectric surface 14 with photoresist24. Photoresist 24 is patterned so that a gap appears in the photoresistto expose dielectric surface 14. The via is to be formed in the areawhere dielectric surface 14 is exposed.

After the photoresist has been deposited and patterned to form anopening, IC 10 is etched to remove material from dielectric interlevel12 below exposed dielectric surface 14. As is well known in the art, afluorine, oxygen, or ozone plasma is typically used in the etchingprocess.

FIG. 2 is a cross-sectional view of IC 10 following the plasma etchstep. Photoresist 24 has also been stripped away. As a result of theplasma etch performed in FIG. 1, various by-products and polymers 28 areformed on a first metal level surface 29 on first metal level 18, whichis accessed from dielectric surface 14 through a via. By-products 28,formed as a result of etching dielectric interlevel 12 are oftendifficult to remove. A process operation referred to as ashing is oftenused to remove by-products 28. An oxygen or ozone plasma 30isotropically etches by-products 28 from the via. In many processes,photoresist 24 (FIG. 1) and polymer by-products 28 are removed in thesame step.

FIG. 3 is a cross-sectional view of IC 10 following the process ofashing. Since the ashing operation involves the use of oxygen, metaloxides 32 are formed overlying first metal level surface 29. To removemetal oxide layer 32, a β-diketone vapor 34, such as Hhfac, isintroduced. For example, when first metal level 18 is copper, Hhfacreacts with copper oxide to form water and the volatile Cu⁺² (hfac)₂complex. Since water is also volatile, CuO 32 is entirely removed fromfirst metal level surface 29 in a vapor phase as shown below:

 CuO+2Hhfac→Cu⁺²(hfac)₂+H₂O

A more complete discussion of β-diketones is presented with regard toFIG. 5, below.

β-diketone vapor 34 removes metal oxides 32 with a minimal loss of firstmetal level surface 29. To better appreciate the action of β-diketonevapor 34, a brief comparison is made to the cleaning action of fluorineand oxygen plasmas 26 and 30, below.

Fluorine and oxygen plasma etchants, 26 and 30, depicted in FIGS. 1 and2 are anisotropic and relatively non-selective. That is, plasmas 26 and30 are directional, removing intended target materials, and a portion ofunintended target materials. IC 10 and a wafer chuck upon which IC 10 ismounted (not shown), must be suitably positioned in an ionizedenvironment to direct the plasmas to intended targets. In FIG. 1, plasma26 is directed perpendicular to dielectric surface 14 to form a via withminimum undercutting beneath photoresist layers 24. In FIG. 2, oxygenplasma 30 is directed to remove polymer layer 28 in the bottom of thevia hole. Metal oxide layer 32 is likewise located in the bottom of thevia. Care must be taken to protect sensitive surfaces that are not to beremoved in the etching process.

Even though the β-diketone vapor is ubiquitous throughout the atmospherein which IC 10 is placed, it works selectively to remove only metaloxide layer 32. In one aspect of the invention the β-diketone is Hhfac.The cleaning by-products formed from the reaction of Hhfac with oxidesof copper and silver are volatile. These volatile by-products are easilyremoved from first metal level surface 29 with a minimal loss of firstmetal level surface 29, and the area of IC 10 without breaking thechamber vacuum prior to the deposition of a subsequent metal layer.

FIG. 4 is a cross-sectional view of IC 10 following the process for theselective, in-situ, cleaning of first metal level surface 29 of metaloxides 32 with β-diketone vapor 34 in an atmosphere free of oxygen, asshown in FIG. 3. First metal level surface 29 has not had an opportunityto form another layer of metal oxide, and is prepared for the subsequentdeposition of a metal level. A second metal layer 36 overlies firstmetal level surface 29 in the via, and dielectric surface 14. Secondmetal layer 36 is deposited on first metal level surface 29, after thein-situ cleaning process shown in FIG. 3, to electrically communicatewith first metal level 18. The in-situ cleaning process helps insurethat a low resistance electrical interconnect, or interface, resultsbetween the two metal structures. Metal layer 36 is selected from thegroup of metals consisting of TiN, TiSi_(x)N_(y), TaSi_(x)N_(y), TaN,WN, WSi_(x)N_(y), Ti, Ta, W, Cu, Al, Ag, and Au. Typically, second metallayer 36 is a barrier metal layer, such as barrier metal layer 20. It isused to prevent the migration of metal atoms from first metal level 18into underlying semiconductor material (not shown). Second metal level36 is conductive to electrically interface with a third metal level 38deposited over second metal level 36. When it is not important toprevent the migration of metal atoms from first metal level 18, thirdmetal level 38 is deposited on first metal level 18 without the barrierlayer, second metal level 36. Further, even when a barrier layer isused, it is standard practice in the industry to identify second metallevel 36 as the combination of second metal level 36 and third metallevel 38 depicted in FIG. 4. Second metal layer 36 and third metal layer38 have been introduced, above, as separate metal layers for thepurposes of clarity, however, from this point on the second metal layeris understood to be the combination of layers 36 and 38.

The relatively simple process of releasing an Hhfac vapor 34 to volatizemetal oxide layer 32, and removing the volatilized by-products with avacuum, is a large improvement in the method of cleaning metal oxides.Typically, no attempt is even made to dean copper surfaces of oxides.Exposure to the copper surface to an uncontrolled atmosphere, as it ismoved between chambers after cleaning, causes the formation of moreoxides on the surface. As a result, the electrical conductivity ofcopper surfaces in IC structures are often degraded. By keeping IC 10 inthe oxygen-free environment, first metal level surface 29 is not allowedto re-oxidize after cleaning and the electrical connection to secondmetal level 36 is improved. Further, since Hhfac vapor 34 selectivelyremoves only metal oxides 32 from first metal level surface 29, aminimum of conductive material is removed from first metal level 18.This is an important consideration in IC fabrication, in many designsthe first metal level is less than 0.5 microns thick.

Hexafluoroacetylacetone or hfac is a particular example of a β-diketone.The prototypical example is the well known compound, acetylacetone oracac. This family of compounds is characterized by a molecular structureinvolving two carbonyl functional groups separated by a single carbonatom to which is attached at least one hydrogen atom. Hence, β-diketonesare also characterized by keto-enol tautomerisms in which the enol formis stabilized by conjugated double bonds. This results in β-diketoneshaving chemical properties of both ketones and enols. In addition, theconjugated nature of the double bonding implies significantdelocalization of π-electrons. These delocahzed electrons readilyinteract with the d-electrons of metal atoms to form coordinationcompounds. In such compounds, due to the presence of the two carbonylgroups, each β-diketone ligand coordinates twice with the metal atom toform a closed ring or chelated structure. Furthermore, the hydrogen atominvolved in the ketoenol tautomerism is weakly bonded and, thuspossesses significant acidic character. Thus, β-diketones readily formstable anions which can be combined with metallic cations to form stablecomplexes. The copper precursor (tmvs)(hfac)Cu(I) is an example of sucha complex, however, many other types of these compounds exist and can beused for MOCVD. The choice of a specific β-diketone as ligand in a MOCVDprecursor is determined by the desirable characteristics of theresulting complex. Typically, such properties are thermal stability,high volatility, etc. Generally, it is found that hfac possesses suchdesirable properties, however, research continues into developing otherβ-diketones having even more desirable characteristics than hfac.

FIG. 5 is a representation of the keto-enol tautomerisms. A compoundsuch as a β-diketone exists in both keto and enol forms. That is, theβ-diketone exists in all three forms, although is generally true thatketo-acids are more stable. There is no preference between theright-most and left-most enol forms. The O and OH groups are notpredisposed in their carbon bonding to favor the formation of eitherenol form. Also in the structural formula of FIG. 5 are bonds to R, R¹,and X. The R and R¹ groups are selected from the set of groupsconsisting of C1 to C6 alkyls, perfluoroalkyls, and other substitutionswhich bond to the carbon atoms. The R and R¹ groups need not be thesame. The number after the “C” refers to the number of carbon atoms inthe alkyl group, for example, a C1 alkyl group contains 1 carbon atom.The X group is selected from the functional group consisting of H, F,CL, Br, I, alkyls, perfluoroalkyls, and substitutions which bond to theCH molecule. In Hhfac, for example, the R and R¹ groups are both F₃, andthe X functional group is H.

FIG. 6 illustrates a system for the selective, in-situ, cleaning ofmetal oxides from a surface on a first metal level of an integratedcircuit. The IC includes a dielectric interlevel with a dielectricsurface, and a plurality of metal levels underlying the dielectricinterlevel. The first metal level surface is accessed through a via fromthe dielectric surface to the first metal level. The system comprises achamber 40 to control an atmosphere to be substantially free of oxygenduring the cleaning and metal deposition process. The formation of metaloxides on the first metal level surface is, thus, minimized. In oneaspect of the invention, chamber 40 is a cluster tool, or series ofconnected chambers sharing the same atmosphere. The system alsocomprises a bubbler 42 to introduce, or deliver, a β-diketone vapor intochamber 40. The system comprises a wafer chuck 44 located inside chamber40, upon which the IC is mounted. Wafer chuck 44 has a predeterminedtemperature to control, or maintain, the temperature of the IC. Theβ-diketone volatilizes metal oxides on the surface of the first metallevel in preparation for an electrical connection to subsequentlydeposited metal levels. FIGS. 1-4 correspond to steps in the process offorming an interconnection in an IC that are carried out in a systemsuch as the one depicted in FIG. 6. As in first metal level 18 of FIGS.1-4, the first metal level of the IC prepared in the above system is ametal selected from the group consisting of copper and silver.

In one aspect of the invention the β-diketone vapor introduced bybubbler 42 is Hhfac, whereby metal oxides from the first metal levelsurface are volatilized for easy removal from chamber 40. Bubbler 42delivers the Hhfac at a pressure of less than approximately 85 Torr at atemperature of approximately 20° C. It is the relative ease to whichHhfac is introduced to chamber 40 that gives the present invention muchof its value.

Bubbler 42 is a sealed ampule containing a β-diketone liquid such asHhfac. The ampule is equipped with a gas inlet tube. The tube isinserted to below the surface of a liquid. A vapor output tube 48 islocated at the top of bubbler 42 to draw away the Hhfac vapor. A carriergas, typically an inert gas such as He, is forced into inlet 46 at apredetermined flow rate and bubbled through the Hhfac. The carrier gasbecomes saturated with the Hhfac vapor. The partial pressure of theHhfac vapor in the carrier gas is determined, or controlled, by thetemperature of the liquid.

FIG. 7 is a graph illustrating the relationship of Hhfac vapor pressureversus inverse temperature. As shown in the graph, at room temperature(20° C.) the corresponding Hhfac vapor pressure is approximately 85Torr. This relationship shows that high vapor pressures can be achievedwith no special preparation of the Hhfac liquid. Referring again to FIG.6, a valve, mass flow controller (MFC), or orifice arrangement 50located between bubbler 42 and chamber 40, is sufficient to control theamount of Hhfac that enters chamber 40.

It is an aspect of the invention that wafer chuck 44 has a temperatureis the range between 100 and 500° C. In this manner, the temperature ofthe IC is maintained in the range between 100 and 450° C. during thecleaning and metal layer deposition processes.

The system further comprises a liquid injector 52 to introduce liquidprecursor compounds including metal into chamber 40. A second metallevel is deposited on the first metal level surface, which is free ofmetal oxides, to facilitate a low resistance electrical connection. Thatis, after the process of cleaning metal oxides with the Hhfac, a liquidprecursor is injected in line 52 to deposit the second metal level. Boththe cleaning and the metal deposition processes are conducted in theoxygen-free environment of chamber 40, so that a minimum number of metaloxides are formed between steps. It is an aspect of the invention thatthe second metal level overlying the first metal level surface is ametal selected from the group consisting of TiN, TiSi_(x)N_(y),TaSi_(x)N_(y), TaN, WN, WSi_(x)N_(y), Ti, Ta, W, Cu, Al, Ag, and Au.

In another embodiment of the invention, a vapor delivery systemintroduces vapor precursor compounds including metal on line 52 intochamber 40. A second metal level is deposited on the first metal levelsurface, which is free of oxides, to facilitate a low resistanceelectrical interconnection. The second metal level overlying the firstmetal level surface is a metal selected from the group consisting ofTiN, TiSi_(x)N_(y), TaSi_(x)N_(y), TaN, WN, WSi_(x)N_(y), Ti, Ta, W, Cu,Al, Ag, and Au.

This system also comprises a pump 54 to create a vacuum pressure inchamber 40. The volatile metal oxides of the first metal level surfaceare removed from chamber 40 through a line 56.

FIG. 8 is a flow chart illustrating steps in a method for selectivelycleaning metal oxides, in-situ, from a surface on a first metal level.Step 70 provides an IC circuit having a dielectric interlevel with adielectric surface, and a plurality of metal levels underlying thedielectric interlevel. A surface on a first metal level is accessedthrough a via from the dielectric surface. Step 72 provides anatmosphere surrounding the IC. Step 74 controls the atmosphere to besubstantially free of oxygen, whereby the formation of metal oxides onthe first metal level surface is minimized. Step 76 introduces aβ-diketone vapor into the atmosphere. Step 78 volatilizes the metaloxides from the first metal level surface using the β-diketone vaporintroduced in step 76. While maintaining the atmosphere established instep 74, step 80 deposits a second metal level overlying the first metallevel surface to electrically interface to the first metal levelsurface, whereby the cleaning process facilitates a low resistanceelectrical connection. The second metal level is a metal selected fromthe group consisting of TiN, TiSi_(x)N_(y), TaSi_(x)N_(y), TaN, WN,WSi_(x)N_(y), Ti, Ta, W, Cu, Al, Ag, and Au. Step 82 is a product, amultilevel interconnected integrated circuit having a first metal levelsurface selectively cleaned, in-situ, of metal oxides with a minimalamount of material removed from the first metal level surface. The firstmetal level surface is cleaned in preparation for an electricalconnection with subsequently deposited metal levels.

It is an aspect of the invention that the first metal level is a metalselected from the group consisting of copper and silver. It is anotheraspect, that step 76 includes using Hhfac as the β-diketone tovolatilize oxides on the conductive interlevel connection surface.Further, step 76 includes delivering the Hhfac at a pressure of lessthan approximately 85 Torr and a temperature of approximately 20° C.

One aspect of the invention includes the further step 84, before step76, of controlling the IC temperature to be in the range between 100 and450° C. Another aspect of the invention includes the further step 86,following step 78, of, creating a vacuum to remove the volatile metaloxides obtained in step 78 from the atmosphere, whereby the cleaningby-products are easily removed from the area of the IC.

The IC, method, and system described above have focused, for the purposeof greater clarity, on preparing a first metal layer to interconnectwith a second, subsequently deposited, metal layer. It is typical tofabricate ICs with a large number of metal layers. Interconnections mustbe made to all these metal layers. It is understood that the Hhfaccleaning and metal deposition process is not limited to an IC havingonly two metal levels. The above described process is repeated for eachmetal level in an IC so that interconnections are made to every metallevel in an IC having a large number of metal levels.

The advantage of the present invention system of cleaning is that it isboth simple and effective. The delivery system and preparation of theHhfac is straightforward so it can be easily integrated into almost anyIC process. This integration allows the cleaning to be conducted in-situso that the IC is not exposed to oxygen prior to the deposition of thenext metal layer. The above method simplifies the cleaning processbecause it is selective in reacting with only the oxides of copper orsilver. Further, the cleaning by-products are volatile, and easilyremoved from the IC environment. Subsequently deposited metal layers canbe deposited from systems using either liquid or vapor precursors. Othervariations and embodiments of the invention will occur to those skilledin the art.

What is claimed is:
 1. In an integrated circuit (IC), including adielectric interlevel with a dielectric surface, and a plurality ofmetal levels underlying the dielectric interlevel, a system for theselective, in-situ, cleaning of metal oxides from a surface on a firstmetal level, accessed through a via from the dielectric surface to thefirst metal level, the system comprising: a chamber to control anatmosphere to be substantially free of oxygen, whereby the formation ofmetal oxides on the first metal level surface is minimized; a bubbler tointroduce a β-diketone vapor into said chamber; and a wafer chucklocated inside said chamber and upon which the IC is mounted, said waferchuck having a predetermined temperature to control the temperature ofthe IC, whereby the β-diketone volatilizes metal oxides on the surfaceof the first metal level, in preparation for an electrical connection tosubsequently deposited metal levels.
 2. A system as in claim 1 in whichthe β-diketone vapor has the following structural formula:

in which the R and R¹ groups are selected from the set of groupsconsisting of C1 to C6 alkyls, perfluoroalkyls, and other substitutions,and the X group is selected from the functional groups consisting of H,F, CL, Br, I, alkyls, perfluoroalkyls, and substitutions.
 3. A system asin claim 2 in which the β-diketone vapor introduced by said bubbler isHhfac, whereby metal oxides from the first metal level surface arevolatilized for easy removal from the said chamber.
 4. A system as inclaim 3 in which said bubbler delivers the Hhfac at a pressure of lessthan approximately 85 Torr at a temperature of approximately 20° C.
 5. Asystem as in claim 3 in which said wafer chuck temperature is in therange between 100 and 500° C.
 6. A system as in claim 3 furthercomprising: e) a liquid injector to introduce liquid precursor compoundsincluding metal into said chamber, whereby a second metal level isdeposited on the first metal level surface, which is free of metaloxides, to facilitate a low resistance electrical connection.
 7. Asystem as in claim 6 in which the liquid precursor compound introducedinto said chamber to form a second metal level overlying the first metallevel surface is selected from the group consisting of TiN,Tisi_(x)N_(y), TaSi_(x)N_(y), TaN, WN, WSi_(x)N_(y), Ti, Ta, W, Cu, Al,Ag, and Au.
 8. A system as in claim 3 further comprising: f) a vapordelivery system to introduce vapor precursor compounds including metalinto said chamber, whereby a second metal level is deposited on thefirst metal level surface, which is free of metal oxides, to facilitatea low resistance electrical connection.
 9. A system as in claim 8 inwhich the vapor precursor compound introduced into said chamber to forma second metal level overlying the first metal level surface is selectedfrom the group consisting of TiN, TiSi_(x)N_(y), TaSi_(x)N_(y), TaN; WN,WSi_(x)N_(y), Ti, Ta, W, Cu, Al, Ag, and Au.
 10. A system as in claim 3further comprising: a pump to create a vacuum in said chamber, wherebythe volatile metal oxides of the first metal level surface are removedfrom said chamber.
 11. A system as in claim 3 in which the first metallevel is selected from the group consisting of copper and silver.